Solvent compositions comprising unsaturated fluorinated hydrocarbons

ABSTRACT

This invention relates to cleaning compositions comprising unsaturated fluorinated hydrocarbons. The invention further relates to use of said cleaning compositions in methods to clean, degrease, deflux, dewater, and deposit fluorolubricant. The invention further relates to novel unsaturated fluorinated hydrocarbons and their use as cleaning compositions and in the methods listed above.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application claims the benefit of priority of U.S. ProvisionalApplication 60/732,771, filed Nov. 1, 2005.

FIELD OF THE INVENTION

This invention relates to cleaning compositions comprising unsaturatedfluorinated hydrocarbons. The invention further relates to use of saidcleaning compositions in methods to clean, degrease, deflux, dewater,and deposit fluorolubricant. The invention further relates to novelunsaturated fluorinated hydrocarbons and their use as cleaningcompositions and in the methods listed above.

BACKGROUND OF THE INVENTION

Chlorofluorocarbon (CFC) compounds have been used extensively in thearea of semiconductor manufacture to clean surfaces such as magneticdisk media. However, chlorine-containing compounds such as CFC compoundsare considered to be detrimental to the Earth's ozone layer. Inaddition, many of the hydrofluorocarbons used to replace CFC compoundshave been found to contribute to global warming. Therefore, there is aneed to identify new environmentally safe solvents for cleaningapplications, such as removing residual flux, lubricant or oilcontaminants, and particles. There is also a need for identification ofnew solvents for deposition of fluorolubricants and for drying ordewatering of substrates that have been processed in aqueous solutions.

The present invention provides new compositions comprising unsaturatedfluorinated hydrocarbons. These compositions have utility in many of theapplications formerly served by CFC compounds. The compositions of thepresent invention possess some or all of the desired properties oflittle or no environmental impact, ability to dissolve oils, greases orlubricants (in particular fluorine-containing lubricants),non-flammability, and ability to dissolve surfactant compounds used inmethods for drying or dewatering.

SUMMARY OF THE INVENTION

Disclosed herein are novel methods of using a composition comprising atleast one unsaturated fluorinated hydrocarbon selected from the groupconsisting of: compounds having the formula E- or Z-R¹CH═CHR², whereinR¹ and R² are, independently, C₁ to C₆ perfluoroalkyl groups, andunsaturated fluorinated hydrocarbons selected from the group consistingof (CF₃)₂CFCH═CH₂, CF₃CF₂CF₂CH═CH₂, CH₂═CFCF₂CF₂CHF₂, CF₂═CHCF₂CH₂CF₃,CF₃CF═C(CF₃)(CH₃), CH₂═CFCH(CF₃)₂, CHF═CHCH(CF₃)₂, CH₂FCH═C(CF₃)₂,CH₃CF═C(CF₃)₂, (CF₃)₂C═CHCH₃, CHF₂CF₂CF═CFCH₃, C₂F₅CF═CHCH₃,CF₃C(CH₃)═CHCF₃, CH₂═CHCF₂CHFCF₃, CH₂═C(CF₃)CH₂CF₃, CF₃CH═CFCH₂CH₃,CF₃CH═C(CH₃)₂, CF₃(CF₂)₃CF═CF₂, CF₃CF₂CF═CFCF₂CF₃, (CF₃)₂C═C(CF₃)₂,(CF₃)₂CFCF═CFCF₃, (CF₃)₂C═CHC₂F₅, (CF₃)₂CFCF═CHCF₃, CF₃CF₂CF₂CF₂CH═CH₂,CH₂═CHC(CF₃)₃, (CF₃)₂C═C(CH₃)(CF₃), CH₂═CFCF₂CH(CF₃)₂,CF₃CF═C(CH₃)CF₂CF₃, CF₃CH═CHCH(CF₃)₂, (CF₃)₂CFCF═CHCH₃,CF₃CF₂CF₂CF═CHCH₃, CH₂═CHCF₂CF₂CF₂CHF₂, (CF₃)₂C═CHCF₂CH₃,CH₂═C(CF₃)CH₂C₂F₅, CF₃CF₂CF₂C(CH₃)═CH₂, CF₃CF₂CF₂CH═CHCH₃,CH₂═CHCH₂CF₂C₂F₅, CF₃CF₂CF═CFC₂H₅, CH₂═CHCH₂CF(CF₃)₂,CF₃CF═CHCH(CF₃)(CH₃), (CF₃)₂C═CFC₂H₅, (CH₃)₂C═CFCF₂CF₃, (CF₃)₂C═C(CH₃)₂,CF₃CF═CFCF₂CF₂C₂F₅, CF₃CF₂CF═CFCF₂C₂F₅, CF₃CH═CFCF₂CF₂C₂F₅,CF₃CF═CHCF₂CF₂C₂F₅, CF₃CF₂CH═CFCF₂C₂F₅, CF₃CF₂CF═CHCF₂C₂F₅,CF₃CF₂CF₂CF₂CF═CHCH₃, CF₃CF₂CF₂CF═CHCH₂CH₃, (CH₃)₂C═CFCF₂CF₂CF₃,cyclo-CF₂CH═CHCF₂CF₂CF₂—, cyclo-CF₂CF═CFCF₂CF₂CF₂—, CF₂═CHCF₂Br,CF₂═CFCBrH₂, CHF═CBrCF₃, CHF═CHCBrF₂, CHF═CBrCHF₂, CHBr═CFCF₃,CHBr═CHCF₃, CH2=CBrCF₃, CH₂CFCBrF₂, CFBr═CHCF₃, CFBr═CFCF₃,CH₂═CBrCF₂CF₃, CHBr═CHCF₂CF₃, CH₂═CHCF₂CF₂Br, CH₂═CHCBrFCF₃,CF₃CBr═CFCF₃, CH₃CBr═CHCF₃, CF₃CBr═CHCH₃, (CF₃)₂C═CHBr, CF₃CF═CBrCF₂CF₃,CHF₂CBr═CFC₂F₅, CF₂═CBrCHFC₂F₅, CHBr═CF(CF₂)₂CHF₂, CH₂═CBrCF₂C₂F₅,CF₂═CHCF₂CH₂CBrF₂, (CF₃)₂CFCBr═CH₂, CF₂═C(CH₂Br)CF₃, CH₂═C(CBrF₂)CF₃,(CF₃)₂CHCH═CHBr, (CF₃)₂C═CHCH₂Br, CH₂═CHCF(CF₃)CBrF₂, CF₃CF₂CF₂CBr═CH₂,CF₃(CF₂)₃CBr═CH₂, CHCl═CFCClF₂, CHCl═CClCF₃, CHCl═CHCH₂F, CHCl═CFCH₃,CH₂═CClCH₂F, CHF═CClCH₃, CH₂═CClCClF₂, CH₂═CFCCl₂F, CHCl═CClCHF₂,CHCl═CHCClF₂, CHF═CClCHClF, CCl₂═CFCH₃, CH₂═CClCHClF, CH₂═C(CHF₂)CClF₂,CH₂═CHCF₂CHClF, CHCl═C(CH₃)CF₃, CH₂═CHCHClCF₃, CH₃CF═CHCClF₂,CH₂═CClCF₂CF₃, CHCl═CHCF₂CF₃, CH₂═CHCF₂CF₂Cl, CH₂═CHCClFCF₃,CH₃CCl═CHCF₃, CF₃CCl═CHCH₃, CH₂═CHCClFCHCl₂, CH₂═CClCClFCClF₂,CH₂═CClCH₂CClF₂, CH₂═CHCF₂CHCl₂, CH₂═CHCClFCClF₂, CCl₂═C(CH₃)CF₃,CCl₂═CHCH₂CF₃, CH₂═CFCClFCClF₂, CClF═CHC₂H₅, CHCl═CHCF₂CH₃,CH₂═CClCF₂CH₃, CH₃CH═CHCClF₂, (CF₃)₂C═CHCl, CF₃CH═C(CClF₂)CF₃,CHCl═CHCF₂CClFCF₃, CHCl═CHCF(CClF₂)CF₃, CF₃CF═CClCF₂CF₃,CHCl═CF(CF₂)₂CHF₂, CH₂═CClCF₂C₂F₅, CF₂═CHCF₂CH₂CClF₂, (CF₃)₂CFCCl═CH₂,(CF₃)₂CHCH═CHCl, (CF₃)₂C═CHCH₂Cl, CH₂═CHCF(CF₃)CClF₂, CH₂═CClCF₂CF₂C₂F₅,and CHCl═CHCF₂CF₂C₂F₅.

In one embodiment, the methods disclosed herein are methods of using acompound having the formula E- or Z-R¹CH═CHR², wherein R¹ and R² are,independently, C₁ to C₆ perfluoroalkyl groups, for cleaning an articleor substrate.

In another embodiment is a method for depositing a fluorolubricant on asurface comprising: (a) combining a fluorolubricant and a solventcomprising an unsaturated fluorinated hydrocarbon selected from thegroup consisting of:

-   -   (i) unsaturated fluorinated hydrocarbons having the formula E-        or Z-R¹CH═CHR², wherein R¹ and R² are, independently, C₁ to C₆        perfluoroalkyl groups; and    -   (ii) unsaturated fluorinated hydrocarbons selected from the        group consisting of (CF₃)₂CFCH═CH₂, CF₃CF₂CF₂CH═CH₂,        CH₂═CFCF₂CF₂CHF₂, CF₂═CHCF₂CH₂CF₃, CF₃CF═C(CF₃)(CH₃),        CH₂═CFCH(CF₃)₂, CHF═CHCH(CF₃)₂, CH₂FCH═C(CF₃)₂, CH₃CF═C(CF₃)₂,        (CF₃)₂C═CHCH₃, CHF₂CF₂CF═CFCH₃, C₂F₅CF═CHCH₃, CF₃C(CH₃)═CHCF₃,        CH₂═CHCF₂CHFCF₃, CH₂═C(CF₃)CH₂CF₃, CF₃CH═CFCH₂CH₃,        CF₃CH═C(CH₃)₂, CF₃(CF₂)₃CF═CF₂, CF₃CF₂CF═CFCF₂CF₃,        (CF₃)₂C═C(CF₃)₂, (CF₃)₂CFCF═CFCF₃, (CF₃)₂C═CHC₂F₅,        (CF₃)₂CFCF═CHCF₃, CF₃CF₂CF₂CF₂CH═CH₂, CH₂═CHC(CF₃)₃,        (CF₃)₂C═C(CH₃)(CF₃), CH₂═CFCF₂CH(CF₃)₂, CF₃CF═C(CH₃)CF₂CF₃,        CF₃CH═CHCH(CF₃)₂, (CF₃)₂CFCF═CHCH₃, CF₃CF₂CF₂CF═CHCH₃,        CH₂═CHCF₂CF₂CF₂CHF₂, (CF₃)₂C═CHCF₂CH₃, CH₂═C(CF₃)CH₂C₂F₅,        CF₃CF₂CF₂C(CH₃)═CH₂, CF₃CF₂CF₂CH═CHCH₃, CH₂═CHCH₂CF₂C₂F₅,        CF₃CF₂CF═CFC₂H₅, CH₂═CHCH₂CF(CF₃)₂, CF₃CF═CHCH(CF₃)(CH₃),        (CF₃)₂C═CFC₂H₅, (CH₃)₂C═CFCF₂CF₃, (CF₃)₂C═C(CH₃)₂,        CF₃CF═CFCF₂CF₂C₂F₅, CF₃CF₂CF═CFCF₂C₂F₅, CF₃CH═CFCF₂CF₂C₂F₅,        CF₃CF═CHCF₂CF₂C₂F₅, CF₃CF₂CH═CFCF₂C₂F₅, CF₃CF₂CF═CHCF₂C₂F₅,        CF₃CF₂CF₂CF₂CF═CHCH₃, CF₃CF₂CF₂CF═CHCH₂CH₃, (CH₃)₂C═CFCF₂CF₂CF₃,        cyclo-CF₂CH═CHCF₂CF₂CF₂—, cyclo-CF₂CF═CFCF₂CF₂CF₂—, CF₂═CHCF₂Br,        CF₂═CFCBrH₂, CHF═CBrCF₂, CHF═CHCBrF₂, CHF═CBrCHF₂, CHBr═CFCF₃,        CHBr═CHCF₃, CH2=CBrCF₃, CH₂CFCBrF₂, CFBr═CHCF₃, CFBr═CFCF₃,        CH₂═CBrCF₂CF₃, CHBr═CHCF₂CF₃, CH₂═CHCF₂CF₂Br, CH₂═CHCBrFCF₃,        CF₃CBr═CFCF₃, CH₃CBr═CHCF₃, CF₃CBr═CHCH₃, (CF₃)₂C═CHBr,        CF₃CF═CBrCF₂CF₃, CHF₂CBr═CFC₂F₅, CF₂═CBrCHFC₂F₅,        CHBr═CF(CF₂)₂CHF₂, CH₂═CBrCF₂C₂F₅, CF₂═CHCF₂CH₂CBrF₂,        (CF₃)₂CFCBr═CH₂, CF₂═C(CH₂Br)CF₃, CH₂═C(CBrF₂)CF₃,        (CF₃)₂CHCH═CHBr, (CF₃)₂C═CHCH₂Br, CH₂═CHCF(CF₃)CBrF₂,        CF₃CF₂CF₂CBr═CH₂, CF₃(CF₂)₃CBr═CH₂, CHCl═CFCClF₂, CHCl═CClCF₃,        CHCl═CHCH₂F, CHCl═CFCH₃, CH₂═CClCH₂F, CHF═CClCH₃, CH₂═CClCClF₂,        CH₂═CFCCl₂F, CHCl═CClCHF₂, CHCl═CHCClF₂, CHF═CClCHClF,        CCl₂═CFCH₃, CH₂═CClCHClF, CH₂═C(CHF₂)CClF₂, CH₂═CHCF₂CHClF,        CHCl═C(CH₃)CF₃, CH₂═CHCHClCF₃, CH₃CF═CHCClF₂, CH₂═CClCF₂CF₃,        CHCl═CHCF₂CF₃, CH₂═CHCF₂CF₂Cl, CH₂═CHCClFCF₃, CH₃CCl═CHCF₃,        CF₃CCl═CHCH₃, CH₂═CHCClFCHCl₂, CH₂═CClCClFCClF₂,        CH₂═CClCH₂CClF₂, CH₂═CHCF₂CHCl₂, CH₂═CHCClFCClF₂,        CCl₂═C(CH₃)CF₃, CCl₂═CHCH₂CF₃, CH₂═CFCClFCClF₂, CClF═CHC₂H₅,        CHCl═CHCF₂CH₃, CH₂═CClCF₂CH₃, CH₃CH═CHCClF₂, (CF₃)₂C═CHCl,        CF₃CH═C(CClF₂)CF₃, CHCl═CHCF₂CClFCF₃, CHCl═CHCF(CClF₂)CF₃,        CF₃CF═CClCF₂CF₃, CHCl═CF(CF₂)₂CHF₂, CH₂═CClCF₂C₂F₅,        CF₂═CHCF₂CH₂CClF₂, (CF₃)₂CFCCl═CH₂, (CF₃)₂CHCH═CHCl,        (CF₃)₂C═CHCH₂Cl, CH₂═CHCF(CF₃)CClF₂, CH₂═CClCF₂CF₂C₂F₅, and        CHCl═CHCF₂CF₂C₂F₅,        to form a lubricant-solvent combination;    -   (b) contacting the combination of lubricant-solvent with the        surface; and    -   (c) evaporating the solvent from the surface to form a        fluorolubricant coating on the surface.

In yet another embodiment is a process for removing at least a portionof water from the surface of a wetted substrate, said processcomprising:

-   -   a) contacting the substrate with the compositions of the present        invention further comprising surfactant, and then    -   b) removing the substrate from contact with said composition.

In yet another embodiment is a composition-comprising an unsaturatedfluorinated hydrocarbon having the formula R¹CH═CHR², wherein R¹ and R²are, independently, C₁ to C₆ perfluoroalkyl groups.

In yet another embodiment is a composition comprising an unsaturatedfluorinated hydrocarbon selected from the group consisting ofCH₂═CClCF₂CF₃, CHCl═CHCF₂CF₃, CHCl═CHCF₂CF₂C₂F₅ and CHBr═CHCF₂CF₃.

Other objects and advantages of the present invention will becomeapparent to those skilled in the art upon reference to the detaileddescription that hereinafter follows.

DETAILED DESCRIPTION OF THE INVENTION

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention. Other features andbenefits of any one or more of the embodiments will be apparent from thefollowing detailed description, and from the claims.

Before addressing details of embodiments described below, some terms aredefined or clarified.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

Applicants specifically incorporate the entire content of all citedreferences in this disclosure. Applicants also incorporate by referencethe co-owned Provisional applications 60/732,396, filed Nov. 1, 2005,60/732,090, filed Nov. 1, 2005, 60/732,292, filed Nov. 1, 2005 and60/732,581, filed Nov. 1, 2005.

Further, when an amount, concentration, or other value or parameter isgiven as either a range, preferred range, or a list of upper preferablevalues and lower preferable values, this is to be understood asspecifically disclosing all ranges formed from any pair of any upperrange limit or preferred value and any lower range limit or preferredvalue, regardless of whether ranges are separately disclosed. Where arange of numerical values is recited herein, unless otherwise stated,the range is intended to include the endpoints thereof, and all integersand fractions within the range. It is not intended that the scope of theinvention be limited to the specific values recited when defining arange.

In one embodiment, the present invention provides compounds having theformula E- or Z-R¹CH═CHR² (Formula I), wherein R¹ and R² are,independently, C₁ to C₆ perfluoroalkyl groups. Examples of R¹ and R²groups include, but are not limited to, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂,CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃, CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃,CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, andC(CF₃)₂CF₂C₂F₅. Exemplary, non-limiting Formula I compounds arepresented in Table 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluorobut-2-ene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E CF₃CH═CHCF₂C₂F₅1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF₃CH═CHCF(CF₃)₂1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14ECF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iECF₃CH═CHCF₂CF—(CF₃)₂1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene F14sECF₃CH═CHCF(CF₃)—C₂F₅1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene F14tECF₃CH═CHC(CF₃)₃1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23EC₂F₅CH═CHCF₂C₂F₅ 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iEC₂F₅CH═CHCF(CF₃)₂1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene F15ECF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-eneF15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene F15tECF₃CH═CH—C(CF₃)₂C₂F₅1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2-ene F24EC₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-eneF24iE C₂F₅CH═CHCF₂CF—(CF₃)₂1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene F24sEC₂F₅CH═CHCF(CF₃)—C₂F₅1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept-3-ene F24tEC₂F₅CH═CHC(CF₃)₃1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-ene F33EC₂F₅CF₂CH═CH—CF₂C₂F₅1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE(CF₃)₂CFCH═CH—CF(CF₃)₂1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-ene F33iEC₂F₅CF₂CH═CH—CF(CF₃)₂1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene F16ECF₃CH═CH(CF₂)₅CF₃1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-ene F16sECF₃CH═CHCF(CF₃)—(CF₂)₂C₂F₅1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2- eneF16tE CF₃CH═CHC(CF₃)₂—CF₂C₂F₅1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene F25EC₂F₅CH═CH(CF₂)₄CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iEC₂F₅CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3- eneF25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)hept-3- ene F34EC₂F₅CF₂CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F34iEC₂F₅CF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4- eneF34sE C₂F₅CF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)oct-4- eneF34tE C₂F₅CF₂CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3- ene F3i4E(CF₃)₂CFCH═CH—(CF₂)₃CF₃1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)oct-3- eneF3i4iE (CF₃)₂CFCH═CH—CF₂CF(CF₃)₂1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3- eneF3i4sE (CF₃)₂CFCH═CH—CF(CF₃)C₂F₅1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)hept-3- eneF3i4tE (CF₃)₂CFCH═CH—C(CF₃)₃1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-ene F26EC₂F₅CH═CH(CF₂)₅CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-3-ene F26sEC₂F₅CH═CHCF(CF₃)—(CF₂)₂C₂F₅1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene F26tE C₂F₅CH═CHC(CF₃)₂—CF₂C₂F₅1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-bis(trifluoromethyl)oct- 3-eneF35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene F35iEC₂F₅CF₂CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)non-4-ene F35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-bis(trifluoromethyl)oct- 4-eneF3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene F3i5iE (CF₃)₂CFCH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct- 3-eneF3i5tE (CF₃)₂CFCH═CH—C(CF₃)₂C₂F₅1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3- ene F44ECF₃(CF₂)₃CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec-5-ene F44iECF₃(CF₂)₃CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-ene F44sE CF₃(CF₂)₃CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-ene F44tE CF₃(CF₂)₃CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,-bis(trifluoromethyl)oct- 3-eneF4i4iE (CF₃)₂CFCF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct- 4-eneF4i4sE (CF₃)₂CFCF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-bis(trifluoromethyl)oct- 4-eneF4i4tE (CF₃)₂CFCF₂CH═CH—C(CF₃)₃1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3- eneF4s4sE C₂F₅CF(CF₃)CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)oct- 4-eneF4s4tE C₂F₅CF(CF₃)CH═CH—C(CF₃)₃1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3- eneF4t4tE (CF₃)₃CCH═CH—C(CF₃)₃1,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)hex-3- ene

In one embodiment, compounds of Formula I may be prepared by contactinga perfluoroalkyl iodide of the formula R¹I with aperfluoroalkyltrihydroolefin of the formula R²CH═CH₂ to form atrihydroiodoperfluoroalkane of the formula R¹CH₂CHIR². Thistrihydroiodoperfluoroalkane can then be dehydroiodinated to formR¹CH═CHR². In another embodiment, the olefin R¹CH═CHR² may be preparedby dehydroiodination of a trihydroiodoperfluoroalkane of the formulaR¹CHICH₂R² formed in turn by reacting a perfluoroalkyl iodide of theformula R²I with a perfluoroalkyltrihydroolefin of the formula R¹CH═CH₂.

In one embodiment, said contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include those fabricated fromstainless steels, in particular of the austenitic type, and thewell-known high nickel alloys such as Monel® nickel-copper alloys,Hastelloy® nickel based alloys and Inconel® nickel-chromium alloys.

In another embodiment, the reaction may take be conducted in semi-batchmode in which the perfluoroalkyltrihydroolefin reactant is added to theperfluoroalkyl iodide reactant by means of a suitable addition apparatussuch as a pump at the reaction temperature.

In one embodiment, the ratio of perfluoroalkyl iodide toperfluoroalkyltrihydroolefin is between about 1:1 to about 4:1. Inanother embodiment, the ratio of perfluoroalkyl iodide toperfluoroalkyltrihydroolefin is between from about 1.5:1 to 2.5:1.Ratios less than 1.5:1 tend to result in large amounts of the 2:1 adductas reported by Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol.4, pages 261-270 (1974).

In one embodiment, the temperature for contacting of said perfluoroalkyliodide with said perfluoroalkyltrihydroolefin is within the range ofabout 150° C. to about 300° C. In another embodiment, the temperature isfrom about 170° C. to about 250° C. In yet another embodiment, thetemperature is from about 180° C. to about 230° C.

In one embodiment, the contact time for the reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin is fromabout 0.5 hour to about 18 hours. In another embodiment, the contacttime is from about 4 to about 12 hours.

In yet another embodiment, the contacting of a perfluoroalkyliodide witha perfluoroalkyltrihydroolefin takes place in the presence of acatalyst. In one embodiment, a suitable catalyst is a Group VIItransition metal complex. Representative Group VII transition metalcomplexes include, without limitation, zero valent NiL₄ complexes,wherein the ligand, L, can be a phosphine ligand, a phosphite ligand, acarbonyl ligand, an isonitrile ligand, an alkene ligand, or acombination thereof. In one such embodiment, the Ni(0)L₄ complex is aNiL₂(CO)₂ complex. In one particular embodiment, the Group VIItransition metal complex is bis(triphenyl phospine)nickel(0) dicarbonyl.In one embodiment, the ratio of perfluoroalkyl iodide toperfluoroalkyltrihydroolefin is between about 3:1 to about 8:1. In oneembodiment, the temperature for contacting of said perfluoroalkyl iodidewith said perfluoroalkyltrihydroolefin in the presence of a catalyst, iswithin the range of about 80° C. to about 130° C. In another embodiment,the temperature is from about 90° C. to about 120° C.

In one embodiment, the contact time for the reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin in thepresence of a catalyst is from about 0.5 hour to about 18 hours. Inanother embodiment, the contact time is from about 4 to about 12 hours.

In one embodiment, the trihydroiodoperfluoroalkane prepared by reactionof the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin maybe used directly in the dehydroiodination step. In another embodiment,the trihydroperfluoroalkane is recovered and purified by distillationprior to the dehydroiodination step.

In one embodiment, the dehydroiodination step is carried out bycontacting the trihydroiodoperfluoroalkane with a basic substance. Inone embodiment, basic substances include alkali metal hydroxides (e.g.,sodium hydroxide or potassium hydroxide), alkali metal oxide (forexample, sodium oxide), alkaline earth metal hydroxides (e.g., calciumhydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkalimetal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueousammonia, sodium amide, or mixtures of basic substances such as sodalime. In another embodiment, the basic substance is sodium hydroxide orpotassium hydroxide.

In one embodiment, contacting of the trihydroiodoperfluoroalkane with abasic substance may take place in the liquid phase. In anotherembodiment, the contacting in the liquid phase further takes place inthe presence of a solvent capable of dissolving at least a portion ofboth reactants. In one embodiment, solvents suitable for thedehydroiodination step include one or more polar organic solvents suchas alcohols (e.g., methanol, ethanol, n-propanol, isopropanol,n-butanol, isobutanol, and tertiary butanol), nitriles (e.g.,acetonitrile, propionitrile, butyronitrile, benzonitrile, oradiponitrile), dimethyl sulfoxide, N,N-dimethylformamide,N,N-dimethylacetamide, or sulfolane. In one embodiment, the solvent ischosen based on the boiling point of the product and the ease ofseparation of traces of the solvent from the product duringpurification. In one embodiment, ethanol or isopropanol are goodsolvents for the reaction.

In one embodiment, the dehydroiodination reaction is carried out byaddition of one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction vessel may be fabricated from glass,ceramic, or metal and is preferably agitated with an impeller orstirring mechanism.

In one embodiment, the temperature for the dehydroiodination reaction isfrom about 10° C. to about 100° C. In another embodiment, thetemperature for the dehydroiodination reaction is from about 20° C. toabout 70° C. In one embodiment, the dehydroiodination reaction iscarried out at ambient pressure. In another embodiment, thedehydroiodination reaction is carried out at reduced or elevatedpressure. In one embodiment of the dehydroiodination reaction thecompound of Formula I is distilled out of the reaction vessel as it isformed.

In another embodiment, the dehydroiodination reaction may be conductedby contacting an aqueous solution of said basic substance with asolution of the trihydroiodoperfluoroalkane in one or more organicsolvents of lower polarity such as an alkane (e.g., hexane, heptane, oroctane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon(e.g., methylene chloride, chloroform, carbon tetrachloride, orperchloroethylene), or ether (e.g., diethyl ether, methyl tert-butylether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane,dimethoxyethane, diglyme, or tetraglyme) in the presence of a phasetransfer catalyst. In one such embodiment, the phase transfer catalystincludes quaternary ammonium halides (e.g., tetrabutylammonium bromide,tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride,dodecyltrimethylammonium chloride, and tricaprylylmethylammoniumchloride), quaternary phosphonium halides (e.g.,triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride),or cyclic polyether compounds known in the art as crown ethers (e.g.,18-crown-6 and 15-crown-5).

In yet another embodiment, the dehydroiodination reaction is conductedin the absence of solvent by adding the trihydroiodoperfluoroalkane to asolid or liquid basic substance.

In one embodiment, the reaction time for the dehydroiodination reactionsare from about 15 minutes to about six hours or more depending on thesolubility of the reactants. In another embodiment, thedehydroiodination reaction requires from about 30 minutes to about threehours for completion.

In one embodiment, the compound of formula I is recovered from thedehydroiodination reaction mixture by phase separation after addition ofwater. In another embodiment, the compound of formula I is recoveredfrom the dehydroiodination reaction mixture by distillation. In yetanother embodiment, the compound of formula I is recovered from thedehydroiodination reaction mixture by a combination of phase separationafter addition of water and distillation.

In one embodiment, the compositions of the present invention maycomprise a single compound of Formula I, for example, one of thecompounds in Table 1. In another embodiment, the compositions maycomprise a combination of compounds of Formula I.

Many of the compounds of Formula I exist as different configurationalisomers or stereoisomers. When the specific isomer is not designated,the present invention is intended to include all single configurationalisomers, single stereoisomers, or any combination thereof. For instance,F11E is meant to represent the E-isomer, Z-isomer, or any combination ormixture of both isomers in any ratio. Another example is F33E, by whichis represented the E-isomer, Z-isomer, or any combination or mixture ofboth isomers in any ratio.

In addition to the inventive compounds described above, unsaturatedfluorinated hydrocarbons presented in Table 2 can be used as cleaningcompositions, or also as cleaning agents, for cleaning surfaces orsubstrates.

TABLE 2 Code Structure Chemical Name HFC-1447fzy (CF₃)₂CFCH═CH₂3,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447fzCF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1- pentene HFC-1447fyccCH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1- pentene HFC-1447czcfCF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1- pentene HFC-1447mytmCF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3- methyl-2-buteneHFC-1447fyz CH₂═CFCH(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene HFC-1447ezz CHF═CHCH(CF₃)₂1,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447qztCH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-3- (trifluoromethyl)-2-buteneHFC-1447syt CH₃CF═C(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-2-butene HFC-1456szt (CF₃)₂C═CHCH₃3-(trifluoromethyl)-4,4,4- trifluoro-2-butene HFC-1456pcyyCHF₂CF₂CF═CFCH₃ 2,3,4,4,5,5-hexafluoro-2- pentene HFC-1456szyCF₃CF₂CF═CHCH₃ 3,4,4,5,5,5-hexafluoro-2- pentene HFC-1456mstzCF₃C(CH₃)═CHCF₃ 1,1,1,4,4,4-hexafluoro-2- methyl-2-butene HFC-1456fzceCH₂═CHCF₂CHFCF₃ 3,3,4,5,5,5-hexafluoro-1- pentene HFC-1456ftmfCH₂═C(CF₃)CH₂CF₃ 4,4,4-trifluoro-2- (trifluoromethyl)-1-buteneHFC-1474mzyf CF₃CH═CFCH₂CH₃ 1,1,1,3-tetrafluoro-2- pentene HFC-1483mztCF₃CH═C(CH₃)₂ 1,1,1-trifluoro-3-methyl-2- butene FC-151-12cCF₃(CF₂)₃CF═CF₂ 1,1,2,3,3,4,4,5,5,6,6,6- dodecafluoro-1-hexene (orperfluoro-1-hexene FC-151-12mcy CF₃CF₂CF═CFCF₂CF₃1,1,1,2,2,3,4,5,5,6,6,6- dodecafluoro-3-hexene (or perfluoro-3-hexene)FC-151-12mmtt (CF₃)₂C═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene FC-151-12mmzz (CF₃)₂CFCF═CFCF₃1,1,1,2,3,4,5,5,5-nonafluoro- 4-(trifluoromethyl)-2- penteneHFC-152-11mmtz (CF₃)₂C═CHC₂F₅ 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene HFC-152-11mmyyz (CF₃)₂CFCF═CHCF₃1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)-2-pentene PFBECF₃CF₂CF₂CF₂CH═CH₂ 3,3,4,4,5,5,6,6,6-nonafluoro- (or HFC-1549fz)1-hexene (or perfluorobutylethylene) HFC-1549fztmm CH₂═CHC(CF₃)₃4,4,4-trifluoro-3,3- bis(trifluoromethyl)-1-butene HFC-1549mmtts(CF₃)₂C═C(CH₃)(CF₃) 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2- butene HFC-1549fycz CH₂═CFCF₂CH(CF₃)₂2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl)-1-pentene HFC-1549mytsCF₃CF═C(CH₃)CF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro- 3-methyl-2-penteneHFC-1549mzzz CF₃CH═CHCH(CF₃)₂ 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene HFC-1558szcc (CF₃)₂CFCF═CHCH₃3,4,5,5,5-pentafluoro-4- trifluoromethyl-2-butene HFC-1558szyCF₃CF₂CF₂CF═CHCH₃ 3,4,4,5,5,6,6,6-octafluoro-2- hexene HFC-1558fzcccCH₂═CHCF₂CF₂CF₂CHF₂ 3,3,4,4,5,5,6,6-octafluoro-2- hexene HFC-1558mmtzc(CF₃)₂C═CHCF₂CH₃ 1,1,1,4,4-pentafluoro-2- (trifluoromethyl)-2-penteneHFC-1558ftmf CH₂═C(CF₃)CH₂C₂F₅ 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene HFC-1567fts CF₃CF₂CF₂C(CH₃)═CH₂3,3,4,4,5,5,5-heptafluoro-2- methyl-1-pentene HFC-1567szzCF₃CF₂CF₂CH═CHCH₃ 4,4,5,5,6,6,6-heptafluoro-2- hexene HFC-1567fzfcCH₂═CHCH₂CF₂C₂F₅ 4,4,5,5,6,6,6-heptafluoro-1- hexene HFC-1567sfyyCF₃CF₂CF═CFC₂H₅ 1,1,1,2,2,3,4-heptafluoro-3- hexene HFC-1567fzfyCH₂═CHCH₂CF(CF₃)₂ 4,5,5,5-tetrafluoro-4- (trifluoromethyl)-1-penteneHFC-1567myzzm CF₃CF═CHCH(CF₃)(CH₃) 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene HFC-1567mmtyf (CF₃)₂C═CFC₂H₅ 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene HFC-1576ssty (CH₃)₂C═CFCF₂CF₃3,4,4,5,5,5-hexafluoro-2- methyl-2-pentene HFC-1576mmtt (CF₃)₂C═C(CH₃)₂4-methyl-1,1,1-trifluoro-2- trifluoromethyl-2-butene FC-161-14myyCF₃CF═CFCF₂CF₂C₂F₅ 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene FC-161-14mcyy CF₃CF₂CF═CFCF₂C₂F₅1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene HFC-162-13mzyCF₃CH═CFCF₂CF₂C₂F₅ 1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-2-hepteneHFC-162-13myz CF₃CF═CHCF₂CF₂C₂F₅ 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene HFC-162-13mczy CF₃CF₂CH═CFCF₂C₂F₅1,1,1,2,2,4,5,5,6,6,7,7,7- tridecafluoro-3-heptene HFC-162-13mcyzCF₃CF₂CF═CHCF₂C₂F₅ 1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-hepteneHFC-1659szy CF₃CF₂CF₂CF₂CF═CHCH₃ 3,4,4,5,5,6,6,6-octafluoro-2- hepteneHFC-1678sfzy CF₃CF₂CF₂CF═CHCH₂CH₃ 4,5,5,6,6,7,7,7-octafluoro-3- hepteneHFC-1678ssty (CH₃)₂C═CFCF₂CF₂CF₃ 3,4,4,5,5,6,6,6-octafluoro-2-methyl-2-hexene HFC-C1538zz cyclo-CF₂CH═CHCF₂CF₂CF₂— 3,3,4,4,5,5,6,6-octafluorocyclohexene FC-C151-10y cyclo-CF₂CF═CFCF₂CF₂CF₂—1,2,3,3,4,4,5,5,6,6- decafluorocyclohexene

The compounds listed in Table 2 are available commercially or may beprepared by processes known in the art or as described herein.

In one embodiment, cleaning compositions can comprise a single compoundas listed, for example, in Table 2. In another embodiment, cleaningcompositions may comprise a combination of compounds from Table 2. Inyet another embodiment, cleaning compositions may comprise a combinationof compounds from Table 2 and one or more compounds of Formula I.

Many of the compounds in Table 2 exist as different configurationalisomers or stereoisomers. When the specific isomer is not designated,the present invention is intended to include all single configurationalisomers, single stereoisomers, or any combination thereof. For instance,3,4,4,5,5,6,6,6-octafluoro-2-hexene (HFC-1558szy) is meant to representthe E-isomer, Z-isomer, or any combination or mixture of both isomers inany ratio. Another example is1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (HFC-162-13mczy), bywhich is represented the E-isomer, Z-isomer, or any combination ormixture of both isomers in any ratio.

In addition to the inventive compounds described above, thebromine-containing unsaturated fluorinated hydrocarbons presented inTable 3 can be used as cleaning compositions for cleaning surfaces orsubstrates.

TABLE 3 Structure Chemical Names CF₂═CHCF₂Br3-bromo-1,1,3,3-tetrafluoropropene CF₂═CFCBrH₂3-bromo-1,1,2-trifluoropropene CHF═CBrCF₃2-bromo-1,3,3,3-tetrafluoropropene CHF═CHCBrF₂3-bromo-1,3,3-trifluoropropene CHF═CBrCHF₂2-bromo-1,3,3-trifluoropropene CHBr═CFCF₃1-bromo-2,3,3,3-tetrafluoropropene CHBr═CHCF₃1-bromo-3,3,3-trifluoropropene CH₂═CBrCF₃ 2-bromo-3,3,3-trifluoropropeneCH₂═CFCBrF₂ 3-bromo-2,3,3-trifluoropropene CFBr═CHCF₃1-bromo-1,3,3,3-tetrafluoropropene CFBr═CFCF₃ 1-bromopentafluoropropeneCH₂═CBrCF₂CF₃ 2-bromo-3,3,4,4,4-pentafluoro-1-butene CHBr═CHCF₂CF₃1-bromo-3,3,4,4,4-pentafluoro-1-butene CH₂═CHCF₂CF₂Br4-bromo-3,3,4,4-tetrafluoro-1-butene CH₂═CHCBrFCF₃3-bromo-3,4,4,4-tetrafluoro-1-butene CF₃CBr═CFCF₃2-bromo-1,1,1,3,4,4,4-heptafluoro-2-butene CH₃CBr═CHCF₃2-bromo-4,4,4-trifluoro-2-butene CF₃CBr═CHCH₃2-bromo-1,1,1-trifluoro-2-butene (CF₃)₂C═CHBr1-bromo-3,3,3-trifluoro-2-(trifluoromethyl)- propene CF₃CF═CBrCF₂CF₃3-bromo-1,1,1,2,4,4,5,5,5-nonafluoro-2- pentene CHF₂CBr═CFC₂F₅2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene CF₂═CBrCHFC₂F₅2-bromo-1,1,3,4,4,5,5,5-octafluoro-1-pentene CHBr═CF(CF₂)₂CHF₂1-bromo-2,3,3,4,4,5,5-heptafluoro-1-pentene CH₂═CBrCF₂C₂F₅2-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene CF₂═CHCF₂CH₂CBrF₂5-bromo-1,1,3,3,5,5-hexafluoro-1-pentene (CF₃)₂CFCBr═CH₂2-bromo-3,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-buteneCF₂═C(CH₂Br)CF₃ 2-(bromomethyl)-1,1,3,3,3-pentafluoropropeneCH₂═C(CBrF₂)CF₃ 2-(bromodifluoromethyl)-3,3,3-trifluoropropene(CF₃)₂CHCH═CHBr 1-bromo-4,4,4-trifluoro-3-(trifluoromethyl)-1- butene(CF₃)₂C═CHCH₂Br 4-bromo-1,1,1-trifluoro-2-(trifluoromethyl)-2- buteneCH₂═CHCF(CF₃)CBrF₂ 3-(bromodifluoromethyl)-3,4,4,4-tetrafluoro- 1-buteneCF₃CF₂CF₂CBr═CH₂ 2-bromo-3,3,4,4,5,5,5-heptafluoro-1-penteneCF₃(CF₂)₃CBr═CH₂ 2-bromo-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene

The compounds listed in Table 3 are available commercially or may beprepared by processes known in the art.

1-Bromo-3,3,4,4,4-pentafluoro-1-butene may be prepared by a three-stepsequence beginning with reaction of phosphorous tribromide with3,3,4,4,4-pentafluoro-1-butanol to give4-bromo-1,1,1,2,2-pentafluorobutane. Thermal bromination of4-bromo-1,1,1,2,2-pentafluorobutane at 350-400° C. gives4,4-dibromo-1,1,1,2,2-pentafluorobutane, which may in turn be heatedwith powdered potassium hydroxide to give the desired bromobutene.

2-Bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene may be preparedby addition of bromine to 3,4,4-tetrafluoro-3-(trifluoromethyl)-1-butenefollowed by treatment of the resulting dibromide with ethanolicpotassium hydroxide.

In addition to the inventive compounds described above, thechlorine-containing unsaturated fluorinated hydrocarbons presented inTable 4 can be used as cleaning compositions for cleaning surfaces orsubstrates.

TABLE 4 Structure Chemical Names CHCl═CFCClF₂1,3-dichloro-2,3,3-trifluoro-1-propene CHCl═CClCF₃1,2-dichloro-3,3,3-trifluoro-1-propene CHCl═CHCH₂F1-chloro-3-fluoro-1-propene CHCl═CFCH₃ 1-chloro-2-fluoro-1-propeneCH₂═CClCH₂F 2-chloro-3-fluoro-1-propene CHF═CClCH₃2-chloro-1-fluoro-1-propene CH₂═CClCClF₂2,3-dichloro-3,3-difluoro-1-propene CH₂═CFCCl₂F3,3-dichloro-2,3-difluoro-1-propene CHCl═CClCHF₂1,2-dichloro-3,3-difluoro-1-propene CHCl═CHCClF₂1,3-dichloro-3,3-difluoro-1-propene CHF═CClCHClF2,3-dichloro-1,3-difluoro-1-propene CCl₂═CFCH₃1,1-dichloro-2-fluoro-1-propene CH₂═CClCHClF2,3-dichloro-3-fluoro-1-propene CH₂═C(CHF₂)CClF₂3-chloro-2-(difluoromethyl)-3,3-difluoro-1- propene CH₂═CHCF₂CHClF4-chloro-3,3,4-trifluoro-1-butene CHCl═C(CH₃)CF₃1-chloro-3,3,3-trifluoro-2-methyl-1-propene CH₂═CHCHClCF₃3-chloro-4,4,4-trifluoro-1-butene CH₃CF═CHCClF₂1-chloro-1,1,3-trifluoro-2-butene CH₂═CClCF₂CF₃2-chloro-3,3,4,4,4-pentafluoro-1-butene CHCl═CHCF₂CF₃1-chloro-3,3,4,4,4-pentafluoro-1-butene CH₂═CHCF₂CF₂Cl4-chloro-3,3,4,4-tetrafluoro-1-butene CH₂═CHCClFCF₃3-chloro-3,4,4,4-tetrafluoro-1-butene CH₃CCl═CHCF₃2-chloro-4,4,4-trifluoro-2-butene CF₃CCl═CHCH₃2-chloro-1,1,1-trifluoro-2-butene CH₂═CHCClFCHCl₂3,4,4-trichloro-3-fluoro-1-butene CH₂═CClCClFCClF₂2,3,4-trichloro-3,4,4-trifluoro-1-butene CH₂═CClCH₂CClF₂2,4-dichloro-4,4-difluoro-1-butene CH₂═CHCF₂CHCl₂4,4-dichloro-3,3-1-butene CH₂═CHCClFCClF₂3,4-dichloro-3,4,4-trifluoro-1-butene CCl₂═C(CH₃)CF₃1,1-dichloro-3,3,3-trifluoro-2-methyl-1- propene CCl₂═CHCH₂CF₃1,1-dichloro-4,4,4-trifluoro-1-butene CH₂═CFCClFCClF₂3,4-dichloro-2,3,4,4-tetrafluoro-1-butene CClF═CHC₂H₅1-chloro-1-fluoro-1-butene CHCl═CHCF₂CH₃ 1-chloro-3,3-difluoro-1-buteneCH₂═CClCF₂CH₃ 2-chloro-3,3-difluoro-1- butene CH₃CH═CHCClF₂4-chloro-4,4-difluoro-2-butene (CF₃)₂C═CHCl1-chloro-3,3,3-trifluoro-2-(trifluoromethyl)- propene CF₃CH═C(CClF₂)CF₃2-(chlorodifluoromethyl)-1,1,1,4,4,4- hexafluoro-2-buteneCHCl═CHCF₂CClFCF₃ 1,4-dichloro-3,3,4,5,5,5-hexafluoro-1- penteneCHCl═CHCF(CClF₂)CF₃ 1-chloro-3-(chlorodifluoromethyl)-3,4,4,4-tetrafluoro-1-butene CF₃CF═CClCF₂CF₃3-chloro-1,1,1,2,4,4,5,5,5-nonafluoro-2- pentene CHCl═CF(CF₂)₂CHF₂1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene CH₂═CClCF₂C₂F₅2-chloro-3,3,4,4,5,5,5-heptafluoro-1-pentene CF₂═CHCF₂CH₂CClF₂5-chloro-1,1,3,3,5,5-hexafluoro-1-pentene (CF₃)₂CFCCl═CH₂2-chloro-3,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene(CF₃)₂CHCH═CHCl 1-chloro-4,4,4-trifluoro-3-(trifluoromethyl)- 1-butene(CF₃)₂C═CHCH₂Cl 4-chloro-1,1,1-trifluoro-2-(trifluoromethyl)- 2-buteneCH₂═CHCF(CF₃)CClF₂ 3-(chlorodifluoromethyl)-3,4,4,4-tetrafluoro-1-butene CH₂═CClCF₂CF₂C₂F₅ 2-chloro-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene CHCl═CHCF₂CF₂C₂F₅ 1-chloro-3,3,4,4,5,5,6,6,6-nonafluoro-1- hexene

The compounds listed in Table 4 are available commercially or may beprepared by processes known in the art.

2-Chloro-3,3,4,4,4-pentafluoro-1-butene may be prepared by chlorinationof 3,3,4,4,4-pentafluoro-1-butene to give3,4-dichloro-1,1,1,2,2-pentafluoro-butane followed by reaction of thedichloride with ethanolic potassium hydroxide.

1-Chloro-3,3,4,4,4-pentafluoro-1-butene may be prepared by firstphotochlorinating 1,1,1,2,2-pentafluorobutane to give a mixture ofterminally chlorinated pentafluorobutanes. After separating the4,4-dichloro-1,1,1,2,2-pentafluorobutane by distillation, the dichloroderivative is refluxed with powdered potassium hydroxide to give thedesired 1-chloro-3,3,4,4,4-pentafluoro-1-butene.

1-Chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene may be prepared by reactionof 2,2,3,3,4,4,5,5-octafluoro-1-pentanol withdichlorotriphenylphosphorane followed by reaction of the resultingchloromethyl derivative with base as reported by Zapevalov, et. al. inthe Russian Journal of Organic Chemistry, Vol. 24, pages 1466 to 1472(1988).

2-Chloro-3,3,4,4,5,5,5-heptafluoro-1-pentene may be prepared bychlorination of 3,3,4,4,5,5,5-heptafluoro-1-pentene followed bytreatment of the resulting dichloride with ethanolic potassiumhydroxide.

2-Chloro-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene may beprepared by chlorination of3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene followed by treatmentof the resulting dichloride with ethanolic potassium hydroxide.

2-Chloro-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene may be prepared bychlorination of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene followed bytreatment of the resulting dichloride with ethanolic potassiumhydroxide. 1-Chloro-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene may beprepared by first photochlorinating 1,1,1,2,2,3,3,4,4-nonafluorohexaneto give a mixture of terminally chlorinated pentafluorohexanes. Afterseparating the 6,6-dichloro-1,1,1,2,2,3,3,4,4-nonafluorohexane bydistillation, the dichloro derivative is refluxed with powderedpotassium hydroxide to give the desired1-chloro-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene. Cleaning compositionscan comprise a single unsaturated fluorinated hydrocarbons as listed,for example, in Tables 3 or 4, or may comprise a combination ofcompounds from Table 3, a combination of compounds from Table 4, or,alternatively, a combination of compounds from any of Tables 2, 3 or 4compounds and Formula I compounds. Such combinations of unsaturatedfluorinated hydrocarbons may be utilized to optimize the solvency of asolvent composition for a particular solute.

Many of the compounds in Table 3 and Table 4 exist as differentconfigurational isomers or stereoisomers. When the specific isomer isnot designated, the present invention is intended to include all singleconfigurational isomers, single stereoisomers, or any combinationthereof. For instance, 2-bromo-1,3,3,3-tetrafluoropropene (CHF═CBrCF₃)is meant to represent the E-isomer, Z-isomer, or any combination ormixture of both isomers in any ratio. Another example is1-chloro-1,3,3,3-tetrafluoropropene (CFCl═CHCF₃), by which isrepresented the E-isomer, Z-isomer, or any combination or mixture ofboth isomers in any ratio.

In one embodiment, the compositions disclosed have a Global WarmingPotential (GWP) of not greater than 1000. In another embodiment, thecompositions disclosed have a Global Warming Potential (GWP) of notgreater than 500. In yet another embodiment, the compositions disclosedhave a Global Warming Potential (GWP) of not greater than 150. In stillyet another embodiment, the compositions disclosed have a Global WarmingPotential (GWP) of not greater than 100. In still yet anotherembodiment, the compositions disclosed have a Global Warming Potential(GWP) of not greater than 50. As used herein, “GWP” is measured relativeto that of carbon dioxide and over a 100-year time horizon, as definedin “The Scientific Assessment of Ozone Depletion, 2002, a report of theWorld Meteorological Association's Global Ozone Research and MonitoringProject,” which is incorporated herein by reference.

In one embodiment, the present compositions have an Ozone DepletionPotential (ODP) of not greater than 0.05. In another embodiment, thepresent compositions have an Ozone Depletion Potential (ODP) of notgreater than 0.02. In yet another embodiment, the present compositionshave an Ozone Depletion Potential (ODP) of about zero. As used herein,“ODP” is as defined in “The Scientific Assessment of Ozone Depletion,2002, A report of the World Meteorological Association's Global OzoneResearch and Monitoring Project,” which is incorporated herein byreference.

The amount of the unsaturated fluorinated hydrocarbons contained in thepresent compositions (e.g., from Formula I and Tables 2, 3, or 4) canvary widely, depending upon the particular application, and compositionscontaining more than trace amounts and less than 100% of the compoundare within broad the scope of the present invention.

In one embodiment, the present compositions may further comprise anaerosol propellant. Aerosol propellant may assist in delivering thepresent composition from a storage container to a surface in the form ofan aerosol. Aerosol propellant is optionally included in the presentcomposition in up to about 25 weight percent of the total composition.Representative aerosol propellants comprise air, nitrogen, carbondioxide, difluoromethane (CF₂H₂, HFC-32), trifluoromethane (CF₃H,HFC-23), difluoroethane (CHF₂CH₃, HFC-152a), trifluoroethane (CH₃CF₃,HFC-143a; or CHF₂CH₂F, HFC-143), tetrafluoroethane (CF₃CH₂F, HFC-134a;or CF₂HCF₂H, HFC-134), pentafluoroethane (CF₃CF₂H, HFC-125), andhydrocarbons, such as propane, butanes, or pentanes, or dimethyl ether.

In another embodiment, the present compositions may further comprise atleast one surfactant. The surfactants of the present invention includeall surfactants known in the art for dewatering or drying of substrates.Representative surfactants include alkyl phosphate amine salts (such asa 1:1 salt of 2-ethylhexyl amine and isooctyl phosphate); ethoxylatedalcohols, mercaptans or alkylphenols; quaternary ammonium salts of alkylphosphates (with fluoroalkyl groups on either the ammonium or phosphategroups); and mono- or di-alkyl phosphates of fluorinated amines.Additional fluorinated surfactant compounds are described in U.S. Pat.No. 5,908,822, incorporated herein by reference.

The amount of surfactant included in the dewatering compositions of thepresent invention can vary widely depending on the particular dryingapplication in which said composition will be used, but is readilyapparent to those skilled in the art. In one embodiment, the amount ofsurfactant dissolved in the unsaturated fluorinated hydrocarbon solventis not greater than about 1 weight percent, based on the total weight ofthe surfactant/solvent composition. In another embodiment, largeramounts of surfactant can be used, if after treatment with thecomposition, the substrate being dried is thereafter treated withsolvent containing either no or minimal surfactant. In one embodiment,the amount of surfactant is at least about 50 parts per million (ppm, ona weight basis). In another embodiment, the amount of surfactant is fromabout 100 to about 5000 ppm. In yet another embodiment, the amount ofsurfactant used is from about 200 to about 2000 ppm based on the totalweight of the dewatering composition.

Optionally, other additives may be included in the present compositionscomprising solvents and surfactants for use in dewatering. Suchadditives include compounds having antistatic properties; the ability todissipate static charge from non-conductive substrates such as glass andsilica. Use of an antistatic additive in the dewatering compositions ofthe present invention may be necessary to prevent spots and stains whendrying water or aqueous solutions from electrically non-conductive partssuch as glass lenses and mirrors. Most halocarbon solvents of thepresent invention also have utility as dielectric fluids, i.e., they arepoor conductors of electric current and do not easily dissipate staticcharge. Boiling and general circulation of dewatering compositions inconventional drying and cleaning equipment can create static charge,particularly in the latter stages of the drying process where most ofthe water has been removed from a substrate. Such static charge collectson non-conductive surfaces of the substrate and prevents the release ofwater from the surface. The residual water dries in place resulting inundesirable spots and stains on the substrate. Static charge remainingon substrates can bring out impurities from the cleaning process or canattract impurities such as lint from the air, which results inunacceptable cleaning performance. In one embodiment, desirableantistatic additives are polar compounds, which are soluble in thepresent unsaturated fluorinated hydrocarbon solvent and result in anincrease in the conductivity of the unsaturated fluorinated hydrocarbonsolvent resulting in dissipation of static charge from a substrate. Inanother embodiment, the antistatic additives have a normal boiling pointnear that of the unsaturated fluorinated hydrocarbon solvent and haveminimal to no solubility in water. In yet another embodiment, theantistatic additives have a solubility in water of less than about 0.5weight percent. In one embodiment, the solubility of antistatic agent isat least 0.5 weight percent in unsaturated fluorinated hydrocarbonsolvent. In one embodiment, the antistatic additive is nitromethane(CH₃NO₂).

In one embodiment, the present dewatering composition containing anantistatic additive is effective in both the dewatering and drying andrinse steps of a method to dewater or dry a substrate as describedbelow.

Another embodiment relates to a method for dewatering or drying asubstrate comprising:

-   -   a) contacting the substrate with a composition of the present        invention containing surfactant, thereby dewatering said        substrate and    -   b) recovering the dewatered substrate from the composition.

Many industries use aqueous compositions for the surface treatment ofmetals, ceramics, glasses, and plastics. Cleaning, plating, anddeposition of coatings are often carried out in aqueous media and areusually followed by a step in which residual water is removed. Hot airdrying, centrifugal drying, and solvent-based water displacement aremethods used to remove such residual water.

While hydrofluorocarbons (HFCs) have been proposed as replacements forthe previously used CFC solvents in drying or dewatering applications,many HFCs have limited solvency for water. The use of surfactant, whichassists in removal of water from substrates is therefore necessary inmany drying or dewatering methods. Hydrophobic surfactants have beenadded to dewatering or drying solvents to displace water fromsubstrates.

The primary function of the dewatering or drying solvent (unsaturatedfluorinated hydrocarbon solvent) in a dewatering or drying compositionis to reduce the amount of water on the surface of a substrate beingdried. The primary function of the surfactant is to displace anyremaining water from the surface of the substrate. When the unsaturatedfluorinated hydrocarbon solvent and surfactant are combined, a highlyeffective displacement drying composition is attained.

In one embodiment, drying or dewatering solvents of the disclosureinclude those unsaturated fluorinated hydrocarbon compounds listed inTable 1 and Table 2.

In one embodiment the fluorinated olefins for dewatering or drying of asubstrate from Table 1 and Table 2 have normal boiling points of fromabout 25° C. to about 120° C.

In one embodiment, the surfactant for dewatering and drying is solubleto at least 1 weight percent based on the total solvent/surfactantcomposition weight.

In one embodiment, the dewatering or drying method of the presentdisclosure is very effective in displacing water from a broad range ofsubstrates including metals, such as tungsten, copper, gold, beryllium,stainless steel, aluminum alloys, brass and the like; from glasses andceramic surfaces, such as glass, sapphire, borosilicate glass, alumina,silica such as silicon wafers used in electronic circuits, fired aluminaand the like; and from plastics such as polyolefin (“Alathon”, Rynite®,“Tenite”), polyvinylchloride, polystyrene (Styron),polytetrafluoroethylene (Teflon®), tetrafluoroethylene-ethylenecopolymers (Tefzel®), polyvinylidenefluoride (“Kynar”), ionomers(Surlyn®), acrylonitrile-butadiene-styrene polymers (Kralac®),phenol-formaldehyde copolymers, cellulosic (“Ethocel”), epoxy resins,polyacetal (Delrin®), poly(p-phenylene oxide) (Noryl®), polyetherketone(“Ultrapek”), polyetheretherketone (“Victrex”), poly(butyleneterephthalate) (“Valox”), polyarylate (Arylon®), liquid crystal polymer,polyimide (Vespel®), polyetherimides (“Ultem”), polyamideimides(“Torlon”), poly(p-phenylene sulfide) (“Rython”), polysulfone (“Udel”),and polyaryl sulfone (“Rydel”). In another embodiment, the compositionsfor use in the present dewatering or drying method are compatible withelastomers.

In one embodiment, the disclosure is directed to a process for removingat least a portion of water from, i.e., dewatering, the surface of awetted substrate, which comprises contacting the substrate with theaforementioned dewatering composition, and then removing the substratefrom contact with the dewatering composition. In one embodiment, wateroriginally bound to the surface of the substrate is displaced by solventand/or surfactant and leaves with the dewatering composition. By “atleast a portion of water” is meant at least about 75 weight percent ofwater at the surface of a substrate is removed per immersion cycle. By“immersion cycle” is meant one cycle involving at least a step whereinsubstrate is immersed in the present dewatering composition. Optionally,minimal amounts of surfactant remaining adhered to the substrate can befurther removed by contacting the substrate with surfactant-freehalocarbon solvent. Holding the article in the solvent vapor orrefluxing solvent will further decrease the presence of surfactantremaining on the substrate. Removal of solvent adhering to the surfaceof the substrate is effected by evaporation. Evaporation of solvent atatmospheric or subatmospheric pressures can be employed and temperaturesabove and below the boiling point of the halocarbon solvent can be used.

Methods of contacting the substrate with dewatering composition are notcritical and can vary widely. For example, the substrate can be immersedin the composition, or the substrate can be sprayed with the compositionusing conventional equipment. Complete immersion of the substrate ispreferred as it generally insures contact between the composition andall exposed surfaces of the substrate. However, any other method, whichcan easily provide such complete contact may be used.

The time period over which substrate and dewatering composition arecontacted can vary widely. Usually, the contacting time is up to about 5minutes, however, longer times may be used if desired. In one embodimentof the dewatering process, the contacting time is from about 1 second toabout 5 minutes. In another embodiment, the contacting time of thedewatering process is from about 15 seconds to about 4 minutes.

Contacting temperatures can also vary widely depending on the boilingpoint of the composition. In general, the contacting temperature isequal to or less than the composition's normal boiling point.

In one embodiment, the compositions of the present disclosure mayfurther contain a co-solvent. Such co-solvents are desirable where thepresent compositions are employed in cleaning conventional processresidue from substrates, e.g., removing soldering fluxes and degreasingmechanical components comprising substrates of the present invention.Such co-solvents include alcohols (such as methanol, ethanol,isopropanol), ethers (such as diethyl ether, methyl tertiary-butylether), ketones (such as acetone), esters (such as ethyl acetate, methyldodecanoate, isopropyl myristate and the dimethyl or diisobutyl estersof succinic, glutaric or adipic acids or mixtures thereof), etheralcohols (such as propylene glycol monopropyl ether, dipropylene glycolmonobutyl ether, and tripropylene glycol monomethyl ether), andhydrocarbons (such as pentane, cyclopentane, hexane, cyclohexane,heptane, octane), and hydrochlorocarbons (such astrans-1,2-dichloroethylene). When such a co-solvent is employed with thepresent composition for substrate dewatering or cleaning, it may bepresent in an amount of from about 1 weight percent to about 50 weightpercent based on the weight of the overall composition.

In cleaning apparatuses, including vapor degreasing and vapor defluxingequipment, compositions may be lost during operation through leaks inshaft seals, hose connections, soldered joints and broken lines. Inaddition, the working composition may be released to the atmosphereduring maintenance procedures on equipment. If the composition is not apure component, the composition may change when leaked or discharged tothe atmosphere from the equipment, which may cause the compositionremaining in the equipment to exhibit unacceptable performance.Accordingly, it is desirable to use as a cleaning composition comprisinga single unsaturated fluorinated hydrocarbon.

In one embodiment, the compositions of the present disclosure are usefulas cleaning compositions, cleaning agents, deposition solvents and asdewatering or drying solvents. For proper operation in use,microelectronic components must be cleaned of flux residues, oils andgreases, and particulates that may contaminate the surfaces aftercompletion of manufacture. In another embodiment, the present disclosurerelates to a process for removing residue from a surface or substratecomprising contacting the surface or substrate with a cleaningcomposition or cleaning agent of the present invention and, optionally,recovering the surface or substrate substantially free of residue fromthe cleaning composition or cleaning agent.

In yet another embodiment, the present disclosure relates to a methodfor cleaning surfaces by removing contaminants from the surface. Themethod for removing contaminants from a surface comprises contacting thesurface having contaminants with a cleaning composition of the presentinvention to solubilize the contaminants and, optionally, recovering thesurface from the cleaning composition. The surface is then substantiallyfree of contaminants.

As stated previously, the contaminants or residues that may be removedby the present method include, but are not limited to oils and greases,flux residues, and particulate contaminants.

In one embodiment of the method, the contacting may be accomplished byspraying, flushing, wiping with a substrate e.g., wiping cloth or paper,that has the cleaning composition incorporated in or on it. In anotherembodiment of the method, the contacting may be accomplished by dippingor immersing the disk in a bath of the cleaning composition.

In one embodiment of the method, the recovering is by removing thesurface that has been contacted from the cleaning composition bath (in asimilar manner as described for the method for depositing an afluorolubricant on a surface as described below). In another embodimentof the method, the recovering is by allowing the cleaning compositionthat has been sprayed, flushed, or wiped on the disk to drain away.Additionally, any residual cleaning composition that may be left behindafter the completion of the previous steps may be evaporated in a mannersimilar to that for the deposition method as well.

The method for cleaning a surface may be applied to the same types ofsurfaces as the method for deposition as described below. Semiconductorsurfaces or magnetic media disks of silica, glass, metal or metal oxide,or carbon may have contaminants removed by the method. In the methoddescribed above, contaminant may be removed from a disk by contactingthe disk with the cleaning composition and recovering the disk from thecleaning composition.

In yet another embodiment, the present method also provides methods ofremoving contaminants from a product, part, component, substrate, or anyother article or portion thereof by contacting the article with acleaning composition of the present invention. For the purposes ofconvenience, the term “article” is used herein to refer to all suchproducts, parts, components, substrates, and the like and is furtherintended to refer to any surface or portion thereof. Furthermore, theterm “contaminant” is intended to refer to any unwanted material orsubstance present on the article, even if such substance is placed onthe article intentionally. For example, in the manufacture ofsemiconductor devices it is common to deposit a photoresist materialonto a substrate to form a mask for the etching operation and tosubsequently remove the photoresist material from the substrate. Theterm “contaminant” as used herein is intended to cover and encompasssuch a photo resist material. Hydrocarbon based oils and greases anddioctylphthalate are examples of the contaminants that may be found onthe carbon coated disks.

In one embodiment, the present method comprises contacting the articlewith a cleaning composition of the invention, in a vapor degreasing andsolvent cleaning method. In one such embodiment, vapor degreasing andsolvent cleaning methods consist of exposing an article, preferably atroom temperature, to the vapors of a boiling cleaning composition.Vapors condensing on the object have the advantage of providing arelatively clean, distilled cleaning composition to wash away grease orother contamination. Such processes thus have an additional advantage inthat final evaporation of the present cleaning composition from theobject leaves behind relatively little residue as compared to the casewhere the object is simply washed in liquid cleaning composition.

In another embodiment, for applications in which the article includescontaminants that are difficult to remove, the present methods involveraising the temperature of the cleaning composition above ambient or toany other temperature that is effective in such application tosubstantially improve the cleaning action of the cleaning composition.In one such embodiment, such processes are also generally used for largevolume assembly line operations where the cleaning of the article,particularly metal parts and assemblies, must be done efficiently andquickly.

In one embodiment, the cleaning methods of the present inventioncomprise immersing the article to be cleaned in liquid cleaningcomposition at an elevated temperature. In another embodiment, thecleaning methods of the present invention comprise immersing the articleto be cleaned in liquid cleaning composition at about the boiling pointof the cleaning composition. In one such embodiment, this step removes asubstantial amount of the target contaminant from the article. In yetanother embodiment, this step removes a major portion of the targetcontaminant from the article. In one embodiment, this step is thenfollowed by immersing the article in freshly distilled cleaningcomposition, which is at a temperature below the temperature of theliquid cleaning composition in the preceding immersion step. In one suchembodiment, the freshly distilled cleaning composition is at aboutambient or room temperature In yet another embodiment, the method alsoincludes the step of then contacting the article with relatively hotvapor of the cleaning composition, by exposing the article to vaporsrising from the hot/boiling cleaning composition associated with thefirst mentioned immersion step. In one such embodiment, this results incondensation of the cleaning composition vapor on the article. Incertain preferred embodiments, the article may be sprayed with distilledcleaning composition before final rinsing.

It is contemplated that numerous varieties and types of vapor degreasingequipment are adaptable for use in connection with the present methods.One example of such equipment and its operation is disclosed by U.S.Pat. No. 3,085,918, which is incorporated herein by reference. Theequipment disclosed therein includes a boiling sump for containing acleaning composition, a clean sump for containing distilled cleaningcomposition, a water separator, and other ancillary equipment.

The present cleaning methods may also comprise cold cleaning in whichthe contaminated article is either immersed in the fluid cleaningcomposition of the present invention under ambient or room temperatureconditions or wiped under such conditions with rags or similar objectssoaked in the cleaning composition.

The present invention also relates to a method for depositing afluorolubricant of the invention on a surface, said method comprisingcombining the fluorolubricant with a solvent comprising an unsaturatedfluorinated hydrocarbon of the present invention, contacting saidcombination of fluorolubricant and solvent with the surface andevaporating the solvent to form a fluorolubricant coating on thesurface.

The most advanced, highest recording densities and lowest cost method ofstoring digital information involves writing and reading magnetic fluxpatterns from rotating disks coated with magnetic materials. A magneticlayer, where information is stored in the form of bits, is sputteredonto a metallic support structure. Next an overcoat, usually acarbon-based material, is placed on top of the magnetic layer forprotection and finally a lubricant is applied to the overcoat. Aread-write head flies above the lubricant and the information isexchanged between the head and the magnetic layer. In a relentlessattempt to increase the efficiency of information transfer, hard drivemanufacturers have reduced the distance between the head and themagnetic layer, or fly-height, to less than 100 Angstroms.

Invariably, during normal disk drive application, the head and the disksurface will make contact. To reduce wear on the disk, from both slidingand flying contacts, it must be lubricated.

Fluorolubricants are widely used as lubricants in the magnetic diskdrive industry to decrease the friction between the head and disk, thatis, reduce the wear and therefore minimize the possibility of diskfailure.

There is a need in the industry for improved methods for deposition offluorolubricants. The use of certain solvents, such as CFC-113 andPFC-5060, has been regulated due to their impact on the environment.Therefore, solvents that will be used in this application shouldconsider environmental impact. Also, such solvent must dissolve thefluorolubricant and form a substantially uniform or uniform coating offluorolubricant. Additionally, existing solvents have been found torequire higher fluorolubricant concentrations to produce a giventhickness coating and produce irregularities in uniformity of thefluorolubricant coating.

In one embodiment, the fluorolubricants of the present disclosurecomprise perfluoropolyether (PFPE) compounds, or lubricant comprisingX-1P®, which is a phosphazene-containing disk lubricant. Theseperfluoropolyether compounds are sometimes referred to asperfluoroalkylethers (PFAE) or perfluoropolyalkylethers (PFPAE). ThesePFPE compounds range from simple perfluorinated ether polymers tofunctionalized perfluorinated ether polymers. PFPE compounds ofdifferent varieties that may be useful as fluorolubricant in the presentinvention are available from several sources. In another embodiment,useful fluorolubricants for the present inventive method include but arenot limited to Krytox® GLP 100, GLP 105 or GLP 160 (E. I. du Pont deNemours & Co., Fluoroproducts, Wilmington, Del., 19898, USA); Fomblin®Z-Dol 2000, 2500 or 4000, Z-Tetraol, or Fomblin® AM 2001 or AM 3001(sold by Solvay Solexis S.p.A., Milan, Italy); Demnum™ LR-200 or S-65(offered by Daikin America, Inc., Osaka, Japan); X-1P® (a partiallyfluorinated hyxaphenoxy cyclotriphosphazene disk lubricant availablefrom Quixtor Technologies Corporation, a subsidiary of Dow Chemical Co,Midland, Mich.); and mixtures thereof. The Krytox® lubricants areperfluoroalkylpolyethers having the general structureF(CF(CF₃)CF₂O)_(n)—CF₂CF₃, wherein n ranges from 10 to 60. The Fomblin®lubricants are functionalized perfluoropolyethers that range inmolecular weight from 500 to 4000 atomic mass units and have generalformula X—CF₂—O(CF₂—CF₂—O)_(p)—(CF₂O)_(q)—CF₂—X, wherein X may be—CH₂OH, CH₂(O—CH₂—CH₂)_(n)OH, CH₂OCH₂CH(OH)CH₂OH or —CH₂O—CH₂-piperonyl.The Demnum™ oils are perfluoropolyether-based oils ranging in molecularweight from 2700 to 8400 atomic mass units. Additionally, new lubricantsare being developed such as those from Moresco (Thailand) Co., Ltd,which may be useful in the present inventive method.

The fluorolubricants of the present invention may additionally compriseadditives to improve the properties of the fluorolubricant. X-1P®, whichmay serve as the lubricant itself, is often added to other lower costfluorolubricants in order to increase the durability of disk drives bypassivating Lewis acid sites on the disk surface responsible for PFPEdegradation.

Other common lubricant additives may be used in the fluorolubricants ofthe present inventive methods.

The fluorolubricants of the present invention may further comprise Z-DPA(Hitachi Global Storage Technologies, San Jose, Calif.), a PFPEterminated with dialkylamine end-groups. The nucleophilic end-groupsserve the same purpose as X1P®, thus providing the same stabilitywithout any additive.

The surface on which the fluorolubricant may be deposited is any solidsurface that may benefit from lubrication. Semiconductor materials suchas silica disks, metal or metal oxide surfaces, vapor deposited carbonsurfaces or glass surfaces are representative of the types of surfacesfor which the methods of the present invention are useful. The presentinventive method is particularly useful in coating magnetic media suchas computer drive hard disks. In the manufacture of computer disks, thesurface may be a glass, or aluminum substrate with layers of magneticmedia that is also coated by vapor deposition with a thin (10-50Angstrom) layer of amorphous hydrogenated or nitrogenated carbon. Thefluorolubricant may be deposited on the surface disk indirectly byapplying the fluorolubricant to the carbon layer of the disk.

The first step of combining the fluorolubricant and solvent may beaccomplished in any suitable manner such as mixing in a suitablecontainer such as a beaker or other container that may be used as a bathfor the deposition method. The fluorolubricant concentration in theunsaturated fluorinated hydrocarbon solvent may be from about 0.010percent (wt/wt) to about 0.50 percent (wt/wt).

The step of contacting said combination of fluorolubricant and solventwith the surface may be accomplished in any manner appropriate for saidsurface (considering the size and shape of the surface). A hard drivedisk must be supported in some manner such as with a mandrel or someother support that may fit through the hole in the center of the disk.The disk will thus be held vertically such that the plane of the disk isperpendicular to the solvent bath. The mandrel may have different shapesincluding but not limited to, a cylindrical bar, or a V-shaped bar. Themandrel shape will determine the area of contact with the disk. Themandrel may be constructed of any material strong enough to hold thedisk, including but not limited to metal, metal alloy, plastic or glass.Additionally, a disk may be supported vertically upright in a wovenbasket or be clamped into a vertical position with 1 or more clamps onthe outer edge. The support may be constructed of any material with thestrength to hold the disk, such as metal, metal alloy, plastic or glass.However the disk is supported, the disk will be lowered into a containerholding a bath of the fluorolubricantisolvent combination. The bath maybe held at room temperature or be heated or cooled to temperaturesranging from about 0° C. to about 50° C.

Alternatively, the disk may be supported as described above and the bathmay be raised to immerse the disk. In either case, the disk may then beremoved from the bath (either by lowering the bath or by raising thedisk). Excess fluorolubricantisolvent combination can be drained intothe bath.

Either of the methods for contacting the fluorolubricant/solventcombination with the disk surface of either lowering the disk into abath or raising a bath to immerse the disk are commonly referred to asdip coating. Other methods for contacting the disk with thefluorolubricantisolvent combination may be used in the present inventivemethod, including spraying or spin coating.

When the disk is removed from the bath, the disk will have a coating offluorolubricant and some residual solvent (unsaturated fluorinatedhydrocarbon) on its surface. The residual solvent may be evaporated.Evaporation is usually performed at room temperature. However, othertemperatures both above and below room temperature may be used as wellfor the evaporation step. Temperatures ranging from about 0° C. to about100° C. may be used for evaporation.

The surface, or the disk if the surface is a disk, after completion ofthe coating method, will be left with a substantially uniform or uniformcoating of fluorolubricant that is substantially free of solvent. Thefluorolubricant may be applied to a thickness of less than about 300 nm,and alternately to a thickness of about 100 to about 300 nm.

A uniform fluorolubricant coating is desired for proper functioning of adisk and so areas of varying fluorolubricant thickness are undesirableon the surface of the disk. As more and more information is being storedon the same size disk, the read/write head must get closer and closer tothe disk in order to function properly. If irregularities due tovariation in coating thickness are present on the surface of the disk,the probability of contact of the head with these areas on the disk ismuch greater. While there is a desire to have enough fluorolubricant onthe disk to flow into areas where it may be removed by head contact orother means, coating that is too thick may cause “smear,” a problemassociated with the read/write head picking up excess fluorolubricant.

One specific coating thickness irregularity observed in the industry isthat known as the “rabbit ears” effect. These irregularities arevisually detected on the surface of the disk after deposition of thefluorolubricant using the existing solvent systems. When the disk iscontacted with the solution of fluorolubricant in solvent and thenremoved from the solution, any points where the solution may accumulateand not drain readily develop drops of solution that do not readilydrain off. One such point of drop formation is the contact point (orpoints) with the mandrel or other support device with the disk. When aV-shaped mandrel is used, there are two contact points at which themandrel contacts the inside edge of the disk. When solution offluorolubricant forms drops in these locations that do not drain offwhen removed from the bath, an area of greater thickness offluorolubricant is created when the solvent evaporates. The two pointsof contact with the disk produces what is known as a “rabbit ears”effect, because the areas of greater fluorolubricant thickness produce apattern resembling rabbit ears visually detectable on the disk surface.

When dip coating is used for depositing fluorolubricant on the surface,the pulling-up speed (speed at which the disk is removed from the bath),and the density of the fluorolubricant and the surface tension arerelevant for determining the resulting film thickness of thefluorolubricant. Awareness of these parameters for obtaining the desiredfilm thickness is required. Details on how these parameters effectcoatings are given in, “Dip-Coating of Ultra-Thin Liquid Lubricant andits Control for Thin-Film Magnetic Hard Disks” in IEEE Transactions onMagnetics, vol. 31, no. 6, November 1995.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While the compositions and methods of this invention havebeen described in terms of preferred embodiments, it will be apparent tothose of skill in the art that variations may be applied to thecompositions and methods and in the steps or in the sequence of steps ofthe method described herein without departing from the concept, spirit,and scope of the invention. More specifically, it will be apparent thatcertain cleaning compositions or cleaning agents which are chemicallyrelated may be substituted for the compositions described herein whilethe same or similar results would be achieved. All such similarsubstitutes and modifications apparent to those skilled in the art aredeemed to be within the spirit, scope, and concept of the invention asdefined by the appended claims.

EXAMPLES

The present invention is further defined in the following Examples. Itshould be understood that these Examples, while indicating preferredembodiments of the invention, are given by way of illustration only.From the above discussion and these Examples, one skilled in the art canascertain the preferred features of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various uses andconditions.

Example 1 Synthesis of 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene(F14E) Synthesis of C₄F₉CH₂CHICF₃

Perfluoro-n-butyliodide (180.1 gm, 0.52 moles) and2,2,2-trifluoropropene (25.0 gm, 0.26 moles) were added to a 400 mlHastelloy™ shaker tube and heated to 200° C. for 8 hours underautogenous pressure, which increased to a maximum of 428 psig (3.05Mpa). The product was collected at room temperature. The above reactionwas carried out again at these conditions and the products combined. Itwas then repeated doubling the amount of perfluoro-n-butyliodide and2,2,2-trifluoropropene in the same 400 ml reactor. In this case thepressure increased to 573 psig (3.85 Mpa). The products of the threereactions were combined and distilled to give 322.4 gm of C₄F₉CH₂CHICF₃(52.2°/35 mm) in 70% yield.

Conversion of C₄F₉CH₂CHICF₃ to F14E

C₄F₉CH₂CHICF₃ (322.4 gm, 0.73 moles) was added dropwise via additionfunnel to a 2 L round bottom flask equipped with stir a bar andconnected to a packed distillation column and still head. The flaskcontained isopropyl alcohol (95 ml), KOH (303.7 gm, 0.54 moles) andwater (303 ml). Product was collected, washed with sodium metabisulfite,water, dried with MgSO₄ and distilled through a 6″ column filled withglass helices. The product, F14E (173.4 gm, 76%) boils at 78.2° C. Itwas characterized by ¹⁹F NMR (δ−66.7 (CF₃, m, 3F), −81.7 (CF₃, m 3F),−124.8 (CF₂, m, 2F), −126.4 (CF₂, m, 2F), and −114.9 ppm (CF₂, m, 2F))¹H NMR (δ 6.4{tilde over (5)}) in chloroform-d solution.

Example 2 Synthesis of1,1,1,2,2,5,5,6,6,7,7,8,8-tetradecafluorooct-3-ene (F24E) Synthesis ofC₄F₉CHICH₂C₂F₅

Perfluoroethyliodide (220 gm, 0.895 mole) and3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene (123 gm, 0.50 mole) were added toa 400 ml Hastelloy™ shaker tube and heated to 200° C. for 10 hours underautogenous pressure. The product from this and two others carried outunder similar conditions were combined and washed with two 200 mLportions of 10 wt % aqueous sodium bisulfite. The organic phase wasdried over calcium chloride and then distilled to give 277.4 gm ofC₄F₉CH₂CHICF₃ (79-81° C./67-68 mm Hg) in 37% yield.

Conversion of C₄F₉CHICH₂C₂F₅ to F24E

A 1 L round bottom flask equipped with a mechanical stirrer, additionfunnel, condenser, and thermocouple was charged with C₄F₉CHICH₂C₂F₅(277.4 gm, 0.56 moles) and isopropanol (217.8 g). The addition funnelwas charged with a solution of potassium hydroxide (74.5 g, 1.13 moles)dissolved in 83.8 g of water. The KOH solution was added dropwise to theflask with rapid stirring over the course of about one hour as thetemperature slowly increased from 21° C. to 42° C. The reaction mass wasdiluted with water and the product recovered by phase separation. Theproduct was washed with 50 mL portions of 10 wt % aqueous sodiumbisulfite and water, dried over calcium chloride, and then distilled atatmospheric pressure. The product, F24E (128.7 gm, 63%) boils at 95.5°C. It was characterized by ¹⁹F NMR (δ−81.6 (CF₃, m, 3F), −85.4 (CF₃, m3F), −114.7 (CF₂, m, 2F), −118.1 (CF₂, m, 2F), −124.8 ppm (CF₂, m, 2F),−126.3 ppm (CF₂, m, 2F)) and ¹H NMR (δ 6.48) in chloroform-d solution.

Example 3 Synthesis of CF₃CH═CHCF(CF₃)₂ (F13iE) Synthesis ofCF₃CHICH₂CF(CF₃)₂

(CF₃)₂CFl (265 gm, 0.9 mole) and 2,2,2-trifluoropropene (44.0 gm, 0.45mole) were added to a 400 ml Hastelloy™ shaker tube and heated to 200°C. for 8 hours under autogenous pressure (maximum of 585 psig (4.14MPa)). The product was collected at room temperature to give 110 gm of(CF₃)₂CFCH₂CHICF₃ (76-77° C./200 mm) in 62% yield.

Conversion of (CF₃)₂CFCH₂CHICF₃ to F13iE

A 500 ml round bottom flask was equipped with stir a bar and an additionfunnel and connected to a short path distillation column and dry icetrap. The flask was charged with isopropyl alcohol (50 ml), potassiumhydroxide (109 gm, 1.96 moles), and water (109 ml). (CF₃)₂CFCH₂CHICF₃(109 gm, 0.28 mole) was slowly added dropwise via the addition funnel at42° C. During the addition, the temperature increased from 42 to 55° C.and the product distilled out of the flask. After refluxing for 30minutes, the temperature in the flask increased to 62° C. Product wascollected, washed with water, dried with MgSO₄ and distilled. Theproduct, F13iE (41 gm, 55%), boils at 48-50° C. and was characterized by19F NMR (δ−187.6 (CF, m 1F), −77.1 (CF3, m 6F), −66.3 (CF3, m 3F) inchloroform-d solution.

Example 4 Synthesis of C4F9CHICH2C2F5

3,3,4,4,5,5,6,6,6-Nonafluorohex-1-ene (20.5 gm, 0.0833 mole),bis(triphenyl phosphine)nickel(0) dicarbonyl (0.53 g, 0.0008 mole), andperfluoroethyliodide (153.6 gm, 0.625 mole) were added to a 210 mlHastelloy™ shaker tube and heated at 100° C. for 8 hours underautogenous pressure. Analysis of the product by GC-MS indicated thepresence of C4F9CHICH2C2F5 (64.3 GC area %) and the diadduct (3.3 GCarea %); the conversion of 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene was80.1%.

Example 5

The ability of unsaturated fluoroolefin compounds to dissolve afluorinated oil was determined by adding an amount of the oil to theunsaturated fluoroolefin compound until the mixture became turbid orseparated into two phases. The results in Table 1 show that theunsaturated fluoroolefin compound has high ability to dissolve thefluorinated oil. In addition, a solution of 0.5 wt % of the oil wasprepared in the unsaturated fluoroolefin compound. In this example, theunsaturated fluoroolefin was1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene (F24E). Preweighedmetal coupons were dipped into the solution, the solvent evaporated, andthe coupon re-weighed. Table 5 shows the average coating obtained bythis dip coating process. Thus, unsaturated fluoroolefin compounds canbe used as carrier fluids for the deposition of the fluorinated oil ontoa substrate.

TABLE 5 Oil Solubility in F24E Coating thickness Krytox GPL 102 oilmiscible  2.9 μg/cm² Krytox GPL 106 oil miscible 22.9 μg/cm²

Example 6

Krytox GPL 106 Oil was wiped onto a clean metal coupon, of known weight,with a swab. The coupon was weighed again and then cleaned by immersioninto 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene (F24E) at theroom temperature. The coupon was immersed for 1 minute then air dried.The coupon was then reweighed and the percent of oil removed wasdetermined. These results in Table 6 show that the solvent has excellentefficiency in cleaning fluorinated oils.

TABLE 6 Wt of coupon Percent Wt. of coupon after coating with Wt ofcoupon soil Sample before coating Krytox oil after cleaning removed 110.6782 10.7384 10.6786  99 2 10.4968 10.5328 10.4967 100 3 10.718310.7498 10.7183 100

1. A solvent composition consisting essentially of unsaturatedfluorinated hydrocarbon having the formula R¹CH═CHR², wherein R¹ is CF₃and R² is CF₂CF₂CF₂CF₃.
 2. The composition of claim 1 further consistingessential of a propellant.
 3. The composition of claim 2 wherein thepropellant is selected from the group consisting of air, nitrogen,carbon dioxide, difluoromethane (CF₂H₂, HFC-32), trifluoromethane (CF₃H,HFC-23), difluoroethane (CHF₂CH₃, HFC-152a), trifluoroethane (CH₃CF₃,HFC-143a; or CHF₂CH₂F, HFC-143), tetrafluoroethane (CF₃CH₂F, HFC-134a;or CF₂HCF₂H, HFC-134), pentafluoroethane (CF₃CF₂H, HFC-125), andhydrocarbons, such as propane, butanes, or pentanes, or dimethyl ether.4. The composition of claim 1 further consisting essential of asurfactant.
 5. A method for removing residue from a surface comprising:a. contacting the surface with a composition comprising an unsaturatedfluorinated hydrocarbon having the formula E- or Z-R¹CH═CHR², wherein R¹is CF₃ and R² is CF₂CF₂CF₂CF₃, and b. recovering the surface from thecomposition.
 6. The method of claim 5 wherein said composition furthercomprises an aerosol propellant.
 7. The method of claim 5 wherein saidcomposition further comprises a surfactant.
 8. The method of claim 5wherein said composition further comprises a co-solvent.
 9. The methodof claim 5 wherein the contacting is accomplished by vapor degreasing.10. The method of claim 9, wherein the vapor degreasing is performed by:(i) boiling the composition; and (ii) exposing the article to vapors ofthe boiling cleaning composition.
 11. The method of claim 5, wherein thecontacting is accomplished by immersing the article in said composition,wherein the composition is at a temperature greater than ambient or roomtemperature.
 12. The method of claim 11, wherein the composition is at atemperature of about the boiling point of the composition.
 13. Themethod of claim 5, wherein the contacting is accomplished by wiping thearticle with an object soaked in the composition.
 14. A method fordepositing a fluorolubricant on a surface comprising: (a) combining afluorolubricant and a solvent, said solvent comprising an unsaturatedfluorinated hydrocarbon having the formula E- or Z-R¹CH═CHR², wherein R¹is CF₃ and R² is CF₂CF₂CF₂CF₃, to form a lubricant-solvent combination;(b) contacting the combination of lubricant-solvent with the surface;and (c) evaporating the solvent from the surface to form afluorolubricant coating on the surface.
 15. The method of claim 14,wherein the surface is that of a semiconductor material, metal, metaloxide, vapor deposited carbon, or glass.
 16. The method of claim 14,wherein the surface is that of a magnetic medium.
 17. The method ofclaim 16, wherein the magnetic medium is a computer disk.
 18. The methodof claim 14, wherein the contacting step is accomplished by dipping orimmersing the surface in a bath comprising the fluorolubricant.
 19. Themethod of claim 14, wherein the contacting step is accomplished byspraying or spin coating the surface with the fluorolubricant.
 20. Themethod of claim 14, wherein the fluorolubricant concentration in thelubricant-solvent combination is from about 0.02 weight percent to about0.5 weight percent.
 21. The method of claim 14, wherein the evaporatingstep is accomplished at a temperature of from about 10° C. to about 40°C.
 22. The method of claim 14, wherein the fluorolubricant comprises aperfluoropolyether.
 23. The method of claim 14, wherein thefluorolubricant is selected from the group consisting ofperfluoropolyethers and mixtures thereof.
 24. A process for removing atleast a portion of water from the surface of a wetted substrate, saidprocess comprising: a) contacting the substrate with the composition ofclaim 1, wherein the composition further comprises a surfactant, andthen b) removing the substrate from contact with said composition.